The present invention relates to a process for sizing paper which comprises adding to a suspension containing cellulosic fibres, and optical fillers, a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups, and a sizing promoter comprising a polymer having one or more aromatic groups, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
Dispersions or emulsions of sizing agents are used in papermaking in order to give paper and paper board improved resistance to wetting and penetration by various liquids. The sizing dispersions are usually added to an aqueous suspension containing cellulosic fibres, optional fillers and various additives. The aqueous suspension is fed into a headbox ejecting the suspension onto a wire where a wet web of paper is formed. To the suspension is further commonly added compounds such as starches and microparticulate materials which facilitate the dewatering of the suspension on the wire. The water drained from the wire, referred to as white water, is usually partly recirculated in the papermaking process. The cellulosic suspension contains a certain amount of non-fibrous material, for example fillers, charged polymers, sizing agents and various charged contaminants, i.e. anionic trash, electrolytes, colloidal substances, etc. Part of the non-fibrous material has an influence on the sizing efficiency and will likely impair the sizing efficiency. High amounts of charged compounds such as high contents of salts in the suspension renders a suspension which is increasingly difficult to size, i.e. to obtain a paper with satisfactory sizing properties. Other compounds contained in the suspension which deteriorates sizing are various lipophilic wood extractives which may come from recycled fibres and high yield pulps, i.e. mechanical pulps. An increased amount of added sizing agent often improve sizing, however, leading to higher costs as well an increased accumulation of sizing agents in the white water. The accumulation of non-fibrous material as well as any other component present in the suspension will be even more pronounced in mills where white water is extensively recirculated with the introduction of only low amounts of fresh water into the papermaking process. Thus, it is an objective of the present invention to further improve sizing. Another objective of the present invention is to improve sizing when applying sizes on cellulosic suspensions having high conductivity and/or high amounts of lipophilic wood extractives. Yet further objectives will appear hereinafter.
WO 99/55964 refers to a process for production of paper, where a drainage and retention aid is added to a suspension comprising a cationic or amphoteric polysaccharide having a hydrophobic group. The polysaccharide may be used in conjunction with anionic microparticulate materials and sizing agents.
WO 99/55965 relates to a process for production of paper, where a drainage and retention aid is added to a suspension comprising a cationic organic polymer having an aromatic group. The cationic organic polymer is suitably used together with anionic microparticulate materials.
U.S. Pat. No. 6001166 refers to aqueous alkyl diketen dispersions containing cationic starch and anionic dispersants such as lignin sulphonic acids, condensates of naphthalenesulphonic acid and formaldehyde.
WO 9833979 discloses aqueous dispersions of cellulose-reactive sizing agents comprising cationic organic compounds and anionic stabilisers.
Invention
It has been found that the invention according to the claims surprisingly improves sizing in general and specifically improves sizing of aqueous suspensions containing cellulosic fibres having high conductivities. More specifically, the invention refers to a process for sizing paper which comprises adding to a suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups, and a sizing promoter comprising a polymer having one or more aromatic groups, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
The sizing agent comprised in the dispersion of the present process added to the suspension is suitably any sizing agent known, such as non-cellulose-reactive agents including rosins, e.g. fortified and/or esterified rosins, waxes, fatty acids and resin acid derivatives, e.g. fatty amides and fatty esters, e.g. glycerol triesters of natural fatty acids, and/or cellulose-reactive agents. Preferably, the sizing dispersion contains cellulose-reactive sizing agents. The cellulose-reactive sizing agents comprised in the sizing dispersion can be selected from any cellulose-reactive agents known in the art. Suitably, the sizing agent is selected from hydrophobic ketene dimers, ketene multimers, acid anhydrides, organic isocyanates, carbamoyl chlorides and mixtures thereof, preferably ketene dimers and acid anhydrides, most preferably ketene dimers. Suitable ketene dimers have the general formula (I) below, wherein R1 and R2 represent saturated or unsaturated hydrocarbon groups, usually saturated hydrocarbons, the hydrocarbon groups suitably having from 8 to 36 carbon atoms, usually being straight or branched chain alkyl groups having 12 to 20 carbon atoms, such as hexadecyl and octadecyl groups. The ketene dimers may be liquid at ambient temperature, i.e. at 25xc2x0 C., suitably at 20xc2x0 C. Commonly, acid anhydrides can be characterized by the general formula (II) below, wherein R3 and R4 can be identical or different and represent saturated or unsaturated hydrocarbon groups suitably containing from 8 to 30 carbon atoms, or R3 and R4 together with the xe2x80x94Cxe2x80x94Oxe2x80x94Cxe2x80x94 moiety can form a 5 to 6 membered ring, optionally being further substituted with hydrocarbon groups containing up to 30 carbon atoms. Examples of acid anhydrides which are used commercially include alkyl and alkenyl succinic anhydrides and particularly isooctadecenyl succinic anhydride. 
Suitable ketene dimers, acid anhydrides and organic isocyanates include the compounds disclosed in U.S. Pat. No. 4,522,686, which is hereby incorporated herein by reference. Examples of suitable carbamoyl chlorides include those disclosed in U.S. Pat. No. 3,887,427 which is also incorporated herein by reference.
The sizing dispersion added to the suspension can have a sizing agent content from 0.1 to 50% by weight based on total dispersion/emulsion, suitably over 20% by weight. Dispersions comprising ketene dimer sizing agents may have ketene dimer contents from 5 up to 50% by weight based on total dispersion, preferably from 10 up to 35% by weight. Dispersions, or emulsions, comprising acid anhydride sizing agents may have acid anhydride contents from 0.1 up to 30% by weight based on total dispersion/emulsion, suitably from 1 up to 20% by weight. Dispersions containing non-cellulose reactive sizing agents suitably have sizing agent contents from 5 up to 50% by weight, preferably from 10 up to 35% by weight. The polymer having one or more aromatic groups, i.e. both anionic and cationic polymer having one or more aromatic groups, comprised in the sizing dispersion is suitably present in an amount of from about 0.1% by weight up to about 15% by weight based on sizing agent.
The amount of sizing agent added to the aqueous suspension containing cellulosic fibres can be from 0.01 to 5% by weight, suitably from 0.05 to 1.0% by weight, based on dry weight of cellulosic fibres and optional fillers, where the dosage is dependent on the quality of the pulp or paper to be sized, the sizing agent and the level of sizing.
The sizing dispersion comprising a polymer containing at least one aromatic group can be anionic or cationic, i.e. the dispersing and/or stabilising agents present in the dispersion which can be referred to as the dispersing system have an overall anionic or cationic charge, respectively. The dispersing system can include any agent facilitating the formation of a dispersion or emulsion such as dispersing and/or stabilising agents exemplified by polyelectrolytes, surfactants and electrolytes. Anionic aqueous sizing dispersions may comprise cationic compounds, i.e. cationic polyelectrolytes (cationic or amphoteric polyelectrolytes with an overall cationic charge) and/or cationic surfactants and/or any other cationic compound known to the skilled person provided that the overall charge of the dispersing system is anionic. Cationic aqueous sizing dispersions, on the other hand, can comprise anionic compounds, i.e. anionic polyelectrolytes (anionic or amphoteric polyelectrolytes with an overall anionic charge) and/or anionic surfactants and/or any other anionic compound known to the skilled person provided that the overall charge of the dispersing system is anionic. The anionic or cationic charge of the sizing dispersion can be determined by means of a ZetaMaster S version PCS.
According to the present invention a process is provided which comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent and polymer having one or more aromatic groups, and a sizing promoter comprising a polymer having one or more aromatic groups, the dispersion and sizing promoter being added separately to a suspension. The polymer having one or more aromatic groups can be uncharged or charged, suitably charged, i.e. the polymer can be cationic or anionic, such as being amphoteric and having an overall (net) anionic or cationic charge. The polymer may be an organic polymer suitably derived from natural sources such as polysaccharides, e.g. starches, guar gums, celluloses, chitins, chitosans, glycans, galactans, glucans, xanthan gums, pectins, mannans, dextrins, preferably starches and guar gums, suitable starches including potato, corn, wheat, tapioca, rice, waxy maize, barley, etc, or can be a synthetic polymer such as chain-growth polymers, e.g. vinyl addition polymers like acrylate-, acrylamide- and vinylamide-based polymers, and step-growth polymers, e.g. polyurethanes. Suitably, organic polymers selected from polysaccharides, i.e. starches and vinyl addition polymers like acrylamide-based polymers.
The aromatic group of the polymer can be present in the polymer backbone or, preferably, the aromatic group can be a pendent group attached to or extending from the polymer backbone or be present in a pendent group that is attached to or extending from the polymer backbone (main-chain). The polymer is suitably an organic polymer having an overall anionic or cationic charge.
Suitably, sizing promoter comprises a further polymer having one or more aromatic groups which can be any of those referred to above. Suitably, the net charge of the two polymers containing at least one aromatic group comprised in the sizing promoter are opposite and they are usually added separately to the aqueous suspension. Preferably, the polymer or both polymers comprised in the sizing promoter has/have an aromatic groups with the proviso that the polymer(s) does/do not contain(s) melamine or derivatives of melamine.
According to the present invention the sizing dispersion comprising a polymer having one or more aromatic groups and a sizing promoter comprising a first polymer having one or more aromatic groups and a optionally a further second polymer having one or more aromatic groups, are added separately to the aqueous suspension. By separate addition is meant that the sizing dispersion and the sizing promoter are added at different locations to the cellulosic suspension (thin stock) or at substantially the same location but timely separated. Furthermore, if the sizing promoter comprises two polymers having aromatic groups the are suitably also added separately.
According to one preferred embodiment the present invention refers to a process for sizing paper which comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a polymer having one or more aromatic groups, suitably a cationic organic polymer having one or more aromatic groups and/or an anionic polymer having one or more aromatic groups, the anionic polymer being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, more preferably an anionic polymer having aromatic groups being a step-growth polymer or a naturally occurring aromatic polymer; and a sizing promoter comprising a polymer having one or more aromatic groups being a cationic organic polymers having one or more aromatic groups, such as cationic polysaccharide or cationic vinyl addition polymer, and an anionic polymer having one or more aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, suitably a step-growth polymer or a naturally occurring aromatic polymer such as a naphthalene sulphonate condensation polymer, a polystyrene sulphonate polymer or a modified lignin polymer, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately.
According to a preferred embodiment of the present invention the process for sizing paper comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups and/or an anionic polymer having one or more aromatic groups, the anionic polymer being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, more preferably an anionic polymer having one or more aromatic groups being a step-growth polymer or a naturally occurring aromatic polymer, and a sizing promoter comprising a cationic organic polymer having one or more aromatic groups, and an anionic polymer having one or more aromatic groups selected from step-growth polymers, polysaccharides and naturally occurring aromatic polymers, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
According to yet another preferred embodiment of the present invention the process for sizing paper comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent and an anionic polymer having one or more aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, the amount of added sizing dispersion to the suspension being from about 0.01% up to about 5.0% by weight calculated as sizing agent based on dry fibres, and a sizing promoter comprising a cationic polymer having one or more aromatic groups, suitably being a cationic polysaccharide or a cationic vinyl addition polymer more preferably a cationic polysaccharide, and an anionic polymer having one or more aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, the amount of cationic polymer added to the suspension being from about 0.001% up to about 3% by weight based on dry fibres, and the amount of anionic polymer added to the suspension being from about 0.001% up to about 3% by weight based on dry fibres, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
According to another preferred embodiment of the present invention the process for sizing paper comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups, such as a cationic polysaccharide or a cationic vinyl addition polymer suitably a cationic polysaccharide, and an anionic polymer having one or more aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, the amount of added sizing dispersion to the suspension being from about 0.01% up to about 5.0% by weight calculated as sizing agent based on dry fibres, and a sizing promoter comprising a cationic polymer having one or more aromatic groups, suitably being a cationic polysaccharide or a cationic vinyl addition polymer more preferably a cationic polysaccharide, and an anionic polymer having one or more aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, the amount of cationic polymer added to the suspension being from about 0.001% up to about 3% by weight based on dry fibres, and the amount of anionic polymer added to the suspension being from about 0.001% up to about 3% by weight based on dry fibres, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
According to still a further preferred embodiment the of the present invention the process for sizing paper comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent, like a cellulose-reactive sizing agent, and a cationic organic polymer having an aromatic group and/or an anionic polymer having an aromatic group selected from step-growth polymers, polysaccharides and naturally occurring aromatic polymers, and a sizing promoter comprising a cationic polysaccharide having the structural formula (I): 
wherein P is a residue of a polysaccharide; A is a chain of atoms comprising C and H atoms attaching N to the polysaccharide residue, R1 and R2 are each H or a hydrocarbon group, R3 is an aromatic hydrocarbon group, n is an integer from 2 up to 300000, and Xxe2x88x92 is an anionic counter ion; or a vinyl addition polymer obtained by polymerising a cationic monomer or a monomer mixture comprising a cationic monomer represented by the general formula (II): 
wherein R1 is H or CH3; R2 and R3 are each an alkyl group having from 1 to 3 carbon atoms, A1 is O or NH, B1 is an alkylene group having from 2 to 8 carbon atoms or a hydroxy propylene group, Q is a substituent containing an aromatic group, and Xxe2x88x92 is an anionic counterion; and an anionic polymer having one aromatic group being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer.
According to yet another preferred embodiment of the present invention the process for sizing paper comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having aromatic groups and/or an anionic polymer having aromatic groups, the anionic polymer being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, more preferably an anionic polymer having aromatic groups being a step-growth polymer or a naturally occurring aromatic polymer, and a sizing promoter comprising a cationic polysaccharide having the structural formula (I): 
wherein P is a residue of a polysaccharide; A is a chain of atoms comprising C and H atoms attaching N to the polysaccharide residue, R1 and R2 are each H or a hydrocarbon group, R3 is an aromatic hydrocarbon group, n is an integer from 2 up to 300000, and Xxe2x88x92 is an anionic counter ion, and an anionic polymer having aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
According to yet another preferred embodiment of the present invention the process for sizing paper comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups and/or an anionic polymer having one or more aromatic groups being a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer, and a sizing promoter comprising a cationic vinyl addition polymer obtained by polymerising a cationic monomer or a monomer mixture comprising a cationic monomer represented by the general formula (II): 
wherein R1 is H or CH3; R2 and R3 are each an alkyl group having from 1 to 3 carbon atoms, A1 is O or NH, B1 is an alkylene group having from 2 to 8 carbon atoms or a hydroxy propylene group, Q is a substituent containing an aromatic group, and Xxe2x88x92 is an anionic counterion, and further an anionic polymer having an aromatic group selected from step-growth polymers, polysaccharides and naturally occurring aromatic polymers, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.
Preferably, the anionic polymer having one or more aromatic groups (comprised in the promoter and/or dispersion, suitably in the promoter) is selected from step-growth polymers, polysaccharides and naturally occurring aromatic polymers with the proviso that the anionic polymer is not a melamine sulphonic acid condensation polymer. Usually, the anionic polymer is selected from naphthalene sulphonate condensation polymers like condensated naphthalene sulphonate, polystyrene sulphonate polymers and modified lignin polymers such as sulphonates lignin. Most preferably, the anionic polymer is condensed naphthalene sulphonate or lignin sulphonate.
According to the present invention the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. Although the sizing dispersion may contain the same polymers as comprised in the sizing promoter, significant improvements regarding sizing, is only observed when the sizing promoter and the sizing dispersion are added separately to the cellulosic suspension. By separate addition is meant that the sizing dispersion which may comprise any of the polymers of the sizing promoter and the sizing promoter are added at different locations in the paper mill or at substantially the same location but timely separated. Furthermore, the cationic organic polymer and the anionic polymer forming the sizing promoter are suitably also added separately. Preferably, the anionic polymer having an aromatic group comprised in the sizing promoter is added to the suspension after both the sizing dispersion and the cationic organic polymer.
Cationic Polymer
The cationic organic polymer having one or more aromatic groups of the sizing promoter and which may also be comprised in the sizing dispersion can be derived from natural or synthetic sources, and can be linear, branched or cross-linked. Preferably the cationic polymer is water-soluble or water-dispersable. Examples of suitable cationic polymers include cationic polysaccharides, e.g. starches, guar gums, celluloses, chitins, chitosans, glycans, galactans, glucans, xanthan gums, pectins, mannans, dextrins, preferably starches and guar gums, suitable starches including potato, corn, wheat, tapioca, rice, waxy maize, barley, etc.; cationic synthetic organic polymers such as cationic chain-growth polymers, e.g. cationic vinyl addition polymers like acrylate-, acryl-amide- and vinylamide-based polymers, and cationic step-growth polymers, e.g. cationic polyurethanes. Suitably, cationic organic polymers selected from the group consisting of polysaccharides, i.e. starches, and cationic vinyl addition polymers like acrylamide-based polymers having aromatic groups.
The aromatic group of the cationic organic polymer can be present in the polymer backbone or in a substituent group that is attached to the polymer backbone (main chain), preferably in a substituent group. Examples of suitable aromatic groups include aryl, aralkyl and alkaryl groups, e.g. phenyl, phenylene, naphthyl, xylylene, benzyl and phenylethyl; preferably benzyl, nitrogen-containing aromatic (aryl) groups, e.g. pyridinium and quinolinium, as well as derivatives of these groups. Examples of cationically charged groups that can be present in the cationic polymer as well as in monomers used for preparing the cationic polymer include quaternary ammonium groups, tertiary amino groups and acid addition salts thereof.
According to a preferred embodiment the cationic organic polymer having an aromatic group is selected from cationic polysaccharides. The aromatic group of the polysaccharide can be attached to a heteroatom like nitrogen or oxygen present in the polysaccharide, the heteroatom optionally being charged, for example when it is a nitrogen. The aromatic group can also be attached to a group comprising a heteroatom, e.g. amide, ester or ether, which groups can be attached to the polysaccharide backbone(main-chain), for example via a chain of atoms. Example of suitable aromatic groups and groups comprising an aromatic group include aryl and aralkyl groups, e.g. phenyl, phenylene, naphthyl, phenylene, xylylene, benzyl and phenylethyl; nitrogen-containing aromatic (aryl) groups, e.g. pyridinium and quinolinium, as well as derivatives of these groups where one or more substituents attached to said aromatic groups can be selected from hydroxyl, halides, e.g. chloride, nitro, and hydrocarbon groups having from 1 to 4 carbon atoms.
Preferably, the cationic organic polymer is selected from cationic polysaccharides having the general structural formula (I): 
wherein P is a residue of a polysaccharide; A is a group attaching N to the polysaccharide residue, suitably a chain of atoms comprising C and H atoms, and optionally O and/or N atoms, usually an alkylene group with from 2 to 18 and suitably 2 to 8 carbon atoms, optionally interrupted or substituted by one or more heteroatoms, e.g. O or N, e.g. an alkyleneoxy group or hydroxy propylene group (xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94); R1 and R2 are each H or, preferably, a hydrocarbon group, suitably alkyl, having from 1 to 3 carbon atoms, suitably 1 or 2 carbon atoms; R3 is suitably an aromatic hydrocarbon group including aralkyl groups, e.g. benzyl and phenylethyl groups; n is an integer from about 2 to about 300,000, suitably from 5 to 200,000 and preferably from 6 to 125,000 or, alternatively, R1, R2 and R3 together with N form a aromatic group containing from 5 to 12 carbon atoms; and Xxe2x88x92 is an anionic counterion, usually a halide like chloride.
The aromatic group modified cationic polysaccharide can have a degree of substitution varying over a wide range; the degree of cationic substitution (DSc) can be from 0.01 to 0.5, suitably from 0.02 to 0.3, preferably from 0.025 to 0.2, the degree of aromatic substitution (DSAr) can be from from 0.01 to 0.5, suitably from 0.02 to 0.3, preferably from 0.025 to 0.2, and the degree of anionic substitution (DSA) can be from 0 to 0.2, suitably from 0 to 0.1, preferably from 0 to 0.05.
The polysaccharides can be prepared by subjecting a polysaccharide to cationic and aromatic modification in known manner using one or more agents containing a cationic group and/or a aromatic group, for example by reacting the agent with the polysaccharide in the presence of an alkaline substance such as an alkali metal or alkaline earth metal hydroxide. The polysaccharide to be subjected to cationic and aromatic modification can be non-ionic, anionic, amphoteric or cationic. Suitable modifying agents include non-ionic agents such as, for example aralkyl halides, e.g. benzyl chloride and benzyl bromide; the reaction products of epichlorohydrin and dialkylamines having at least one substituent comprising an aromatic group as defined above, including 3-dialkylamino-1,2-epoxypropanes; and cationic agents such as, for example, the reaction product of epichlorohydrin and tertiary amines having at least one substituent comprising an aromatic group as defined above, including alkaryldialkylamines, e.g. dimethylbenzylamine; arylamines, e.g. pyridine and quinoline. Suitable cationic agents of this type include 2,3-epoxypropyl trialkylammonium halides and halohydroxypropyl trialkylammonium halides, e.g. N-(3-chloro-2-hydroxypropyl)-N-(hydrophobic alkyl)-N,N-di(lower alkyl)ammonium chloride and N-glycidyl-N-(hydrophobic alkyl)-N,N-di(lower alkyl)ammonium chloride where the aromatic group is as defined above, notably octyl, decyl and dodecyl, and the lower alkyl is methyl or ethyl; and halo-hydroxypropyl-N,N-dialkyl-N-alkarylammonium halides and N-glycidyl-N-(alkaryl)-N,N-dialkylammonium chloride, e.g. N-(3-chloro-2-hydroxypropyl)-N-(alkaryl)-N,N-di(lower alkyl)ammonium chloride where the alkaryl and lower alkyl groups are as defined above, particularly N-(3-chloro-2-hydroxypropyl)-N-benzyl-N,N-dimethylammonium chloride; and N-(3-chloro-2-hydroxypropyl) pyridinium chloride. Generally, when using a non-ionic aromatic agent, the polysaccharide is suitably rendered cationic by using any of the cationic agents known in the art before or after the hydrophobic modification. Examples of suitable cationic and/or aromatic modifying agents, aromatic group modified polysaccharides and methods for their preparation include those described in U.S. Pat. Nos. 4,687,519 and 5,463,127; International Patent Application WO 94/24169, European Patent Application No. 189 935; and S. P. Patel, R. G. Patel and V. S. Patel, Starch/Stxc3xa4rke, 41(1989), No. 5, pp. 192-196, the teachings of which are hereby incorporated herein by reference.
According to yet another preferred embodiment the cationic organic polymer is selected from homopolymers and coplymers prepared from one or more monomers comprising at least one monomer having an aromatic group, suitably an ethylenically unsaturated monomer. The cationic polymer may be branched linear or branched. The aromatic group of the cationic polymer can be present in the polymer backbone or, preferably, it can be a pendant group attached to or extending from the polymer backbone or be present in a pendent group that is attached to or extending from polymer backbone. Suitable aromatic (aryl) groups include those comprising a phenyl group, optionally substituted, a phenylene group, optionally substituted, and a naphthyl group, optionally substituted, for example groups having the general formulae xe2x80x94C6H5, xe2x80x94C6H4xe2x80x94, xe2x80x94C6H3xe2x80x94, and xe2x80x94C5H2xe2x80x94, e.g. in the form of phenylene (xe2x80x94C6H4xe2x80x94), xylylene (xe2x80x94CH2xe2x80x94C6H4xe2x80x94CH2xe2x80x94), phenyl (xe2x80x94C6H5), benzyl (xe2x80x94CH2xe2x80x94C6H5), phenethyl (xe2x80x94CH2CH2xe2x80x94C6H5), and substituted phenyl (for example xe2x80x94C6H4xe2x80x94Y, xe2x80x94C6H3Y2, and xe2x80x94C6H2Y3) where one or more substituents (Y) attached to the phenyl ring can be selected from hydroxyl, halides, e.g. chloride, nitro, and hydrocarbon groups having from 1 to 4 carbon atoms.
Preferably, the cationic polymer is a vinyl addition polymer. The term xe2x80x9cvinyl addition polymerxe2x80x9d as used herein, refers to a polymer prepared by addition polymerisation polymerization of one or more vinyl monomers or ethylenically unsaturated monomers which include, for example, acrylamide-based and acrylate-based monomers. Suitably, the cationic polymer is selected from cationic vinyl addition polymers obtained by polymerising a cationic monomer or a monomer mixture comprising a cationic monomer represented by the general formula (II): 
wherein R1 is H or CH3; R2 and R3 are each or, preferably, an alkyl group having from 1 to 3 carbon atoms, usually 1 to 2 carbon atoms; A1 is O or NH; B1 is an alkylene group having from 2 to 8 carbon atoms, suitably from 2 to 4 carbon atoms, or a hydroxy propylene group; Q is a substituent containing an aromatic group, suitably a phenyl or substituted phenyl group, which can be attached to the nitrogen by means of an alkylene group usually having from 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms, and preferably Q is a benzyl group (xe2x80x94CH2xe2x80x94C6H5); and Xxe2x88x92 is an anionic counterion, usually a halide like chloride. Examples of suitable monomers represented by the general formula (II) include quaternary monomers obtained by treating dialkylaminoalkyl (meth)acrylates, e.g. dimethylaminoethyl (meth)-acrylate, diethylaminoethyl (meth)acrylate and dimethylaminohydroxypropyl (meth)acrylate, and dialkylaminoalkyl (meth)acrylamides, e.g. dimethylaminoethyl (meth)acrylamide, diethyl-aminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and diethylamino-propyl (meth)acrylamide, with benzyl chloride. Preferred cationic monomers of the general formula (II) include dimethylaminoethylacrylate benzyl chloride quaternary salt and dimethylaminoethylmethacrylate benzyl chloride quaternary salt.
The cationic vinyl addition polymer can be a homopolymer prepared from a cationic monomer having an aromatic group or a copolymer prepared from a monomer mixture comprising a cationic monomer having an aromatic group and one or more copolymerizable monomers. Suitable copolymerizable non-ionic monomers include monomers represented by the general formula (III): 
wherein R4 is H or CH3; R5 and R6 are each H or a hydrocarbon group, suitably alkyl, having from 1 to 6, suitably from 1 to 4 and usually from 1 to 2 carbon atoms; A2 is O or NH; B2 is an alkylene group of from 2 to 8 carbon atoms, suitably from 2 to 4 carbon atoms, or a hydroxy propylene group or, alternatively, A and B are both nothing whereby there is a single bond between C and N (Oxe2x95x90Cxe2x80x94NR5R6). Examples of suitable copolymerizable monomers of this type include (meth)acrylamide; acrylamide-based monomers like N-alkyl (meth)acrylamides and N,N-dialkyl (meth)acrylamides, e.g. N-n-propylacrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide and N-t-butyl (meth)acrylamide; and dialkylaminoalkyl (meth)acrylamides, e.g. dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acryl-amide and diethylaminopropyl (meth)acrylamide; acrylate-based monomers like dialkyl-aminoalkyl (meth)acrylates, e.g. dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate and dimethylaminohydroxypropyl acrylate; and vinylamides, e.g. N-vinylformamide and N-vinylacetamide. Preferred copolymerizable non-ionic monomers include acrylamide and methacrylamide, i.e. (meth)acrylamide, and the main polymer is preferably an acrylamide-based polymer.
Suitable copolymerizable cationic monomers include the monomers represented by the general formula (IV): 
wherein R7 is H or CH3; R8, R9 and R10 are each H or, preferably, a hydrocarbon group, suitably alkyl, having from 1 to 3 carbon atoms, usually 1 to 2 carbon atoms; A3 is O or NH; B3 is an alkylene group of from 2 to 4 carbon atoms, suitably from 2 to 4 carbon atoms, or a hydroxy propylene group, and Xxe2x88x92 is an anionic counterion, usually methylsulphate or a halide like chloride. Examples of suitable cationic copolymerizable monomers include acid addition salts and quaternary ammonium salts of the dialkylaminoalkyl (meth)acrylates and dialkyl-aminoalkyl (meth)acrylamides mentioned above, usually prepared using acids like HCl, H2SO4, etc., or quaternizing agents like methyl chloride, dimethyl sulphate, etc.; and diallyl-dimethylammonium chloride. Preferred copolymerizable cationic monomers include dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt and diallyldimethyl-ammonium chloride. Copolymerizable anionic monomers like acrylic acid, methacrylic acid, various sulfonated vinyl addition monomers, etc. can also be employed and, preferably, in minor amounts.
The cationic vinyl addition polymer can be prepared from a monomer mixture generally comprising from 1 to 99 mole %, suitably from 2 to 50 mole % and preferably from 5 to 20 mole % of cationic monomer having an aromatic group, preferably represented by the general formula (II), and from 99 to 1 mole %, suitably from 98 to 50 mole %, and preferably from 95 to 80 mole % of other copolymerizable monomers which preferably comprises acrylamide or methacrylamide ((meth)acrylamide), the monomer mixture suitably comprising from 98 to 50 mole % and preferably from 95 to 80 mole % of (meth)acrylamide, the sum of percentages being 100.
The caionic polymer can also be selected from polymers prepared by condensation reaction of one or more monomers containing an aromatic group. Examples of such monomers include toluene diisocyanates, bisphenol A, phthalic acid, phthalic anhydride, etc., which can be used in the preparation of cationic polyurethanes, cationic polyamide-amines, etc.
Alternatively the cationic polymer can be a polymer subjected to aromatic modification using an agent containing an aromatic group. Suitable modifying agents of this type include benzyl chloride, benzyl bromide, N-(3-chloro-2-hydroxypropyl)-N-benzyl-N,N-dimethylammonium chloride, and N-(3-chloro-2-hydroxypropyl) pyridinium chloride. Suitable polymers for such an aromatic modification include vinyl addition polymers. If the polymer contains a tertiary nitrogen which can be quaternized by the modifying agent, the use of such agents usually results in that the polymer is rendered cationic. Alternatively, the polymer to be subjected to aromatic modification can be cationic, for example a cationic vinyl addition polymer.
Usually the charge density of the cationic polymer is within the range of from 0.1 to 6.0 meqv/g of dry polymer, suitably from 0.2 to 4.0 and preferably from 0.5 to 3.0. The weight average molecular weight of synthetic polymers is usually at least about 500,000, suitably above about 1,000,000 and preferably above about 2,000,000. The upper limit is not critical; it can be about 50,000,000, usually 30,000,000 and suitably 25,000,000.
Anionic Polymer
The anionic polymer having one or more aromatic groups comprised in the sizing promoter and which can be contained in the sizing dispersion is selected from the group consisting of step-growth polymers, polysaccharides and naturally occurring aromatic polymers. The term xe2x80x9cstep-growth polymerxe2x80x9d, as used herein, refers to a polymer obtained by step-growth polymerization, also being referred to as step-reaction polymer and step-reaction polymerization, respectively. Preferably the anionic polymer has an aromatic group with the proviso that the anionic polymer is not a melamine sulphonic acid condensation polymer. The anionic polymer can be a step-growth polymer or a naturally occurring aromatic polymer. The anionic polymers according to the invention can be linear, branched or cross-linked. Preferably the anionic polymer is water-soluble or water-dispersable. The anionic polymer is preferably organic.
Preferred anionic aromatic polymers are naphthalene sulphonate condensation polymers, polystyrene sulphonate polymers and modified lignin polymers, even more preferred are naphthalene sulphonate condensation polymers like condensated naphthalene sulphonate, and modified lignin polymers such as lignin sulphonate.
The aromatic group of the anionic polymer can be present in the polymer backbone or in a substituent group that is attached to the polymer backbone (main chain). Examples of suitable aromatic groups include aryl, aralkyl and alkaryl groups and derivatives thereof, e.g. phenyl, tolyl, naphthyl, phenylene, xylylene, benzyl, phenylethyl and derivatives of these groups. Examples of anionically charged groups that can be present in the anionic polymer as well as in the monomers used for preparing the anionic polymer include groups carrying an anionic charge and acid groups carrying an anionic charge when dissolved or dispersed in water, the groups herein collectively being referred to as anionic groups, such as phosphate, phosphonate, sulphate, sulphonic acid, sulphonate, carboxylic acid, carboxylate, alkoxide and phenolic groups, i.e. hydroxy-substituted phenyls and naphthyls. Groups carrying an anionic charge are usually salts of an alkali metal, alkaline earth or ammonia.
Examples of suitable anionic step-growth polymerization products according to the present invention include condensation polymers, i.e. polymers obtained by step-growth condensation polymerization, e.g. condensates of an aldehyde such as formaldehyde with one or more aromatic compounds containing one or more anionic groups, specifically condensated naphthalene sulphonate type polymers, and optional other co-monomers useful in the condensation polymerization such as urea. Examples of suitable aromatic compounds containing anionic groups include phenolic and naphtholic compounds such as phenol, naphthol, resorcinol and derivatives thereof, aromatic acids and salts thereof such as phenylic, phenolic, naphthylic and naphtholic acids and salts, usually sulphonic acids and sulphonates, e.g. benzene sulphonic acid and sulphonate, xylen sulphonic acid and sulphonates, naphthalene sulphonic acid and sulphonate, phenol sulphonic acid and sulphonate.
Examples of further suitable anionic step-growth polymerization products according to the present invention include addition polymers, i.e. polymers obtained by step-growth addition polymerization, e.g. anionic polyurethanes prepared from a monomer mixture comprising aromatic isocyanates and/or aromatic alcohols. Examples of suitable aromatic isocyanates include diisocyanates, e.g. toluene-2,4- and 2,6-diisocyanates and diphenyl-methane-4,4xe2x80x2-diisocyanate. Examples of suitable aromatic alcohols include dihydric alcohols, i.e. diols, e.g. bisphenol A, phenyl diethanol amine, glycerol monoterephthalate and tri-methylolpropane monoterephthalate. Monohydric aromatic alcohols such as phenol and derivaties thereof may also be employed. The monomer mixture can also contain non-aromatic isocyanates and/or alcohols, usually diisocyanates and diols, for example any of those known to be useful in the preparation of polyurethanes. Examples of suitable monomers containing anionic groups include the monoester reaction products of triols, e.g. trimethylolethane, trimethylolpropane and glycerol, with dicarboxylic acids or anhydrides thereof, e.g. succinic acid and anhydride, terephthalic acid and anhydride, such as glycerol monosuccinate, glycerol monoterephthalate, trimethylolpropane monosuccinate, trimethylolpropane monoterephthalate, N,N-bis-(hydroxyethyl)-glycine, di-(hydroxy-methyl)propionic acid, N,N-bis-(hydroxyethyl)-2-aminoethanesulfonic acid, and the like, optionally and usually in combination with reaction with a base, such as alkali metal and alkaline earth hydroxides, e.g. sodium hydroxide, ammonia or an amine, e.g. triethylamine, thereby forming an alkali metal, alkaline earth or ammonium counter-ion.
Examples of suitable anionic chain-growth polymerization products according to the invention include anionic vinyl addition polymers obtained from a mixture of vinylic or ethylenically unsaturated monomers comprising at least one monomer having an aromatic group and at least one monomer having an anionic group, usually co-polymerized with non-ionic monomers such as acrylate- and acrylamide-based monomers. Examples of suitable anionic monomers include (meth)acrylic acid and paravinyl phenol (hydroxy styrene).
Examples of suitable anionic polysaccharides include starches, guar gums, celluloses, chitins, chitosans, glycans, galactans, glucans, xanthan gums, pectins, mannans, dextrins, preferably starches, guar gums and cellulose derivatives, suitable starches including potato, corn, wheat, tapioca, rice, waxy maize and barley, preferably potato. The anionic groups in the polysaccharide can be native and/or introduced by chemical treatment. The aromatic groups in the polysaccharide can be introduced by chemical methods known in the art.
Examples of suitable (modified) naturally occurring aromatic anionic polymers of this invention include Kraft lignin, such as modified lignin polymers like lignin adducts co-polymerised with formaldehyde and sulphonated lignin, e.g. lignin sulphonate and tannin extracts, i.e. naturally occuring polyphenolic substances that are present in the organic extracts of bark of some wood species.
The weight average molecular weight of the anionic polymer can vary within wide limits dependent on, inter alia, the type of polymer used, and usually it is at least about 500, suitably above about 2,000 and preferably above about 5,000. The upper limit is not critical; it can be about 200,000,000, usually 150,000,000, suitably 100,000,000 and preferably 1,000,000.
The anionic polymer can have a degree of anionic substitution (DSA) varying over a wide range dependent on, inter alia, the type of polymer used; DSA is usually from 0.01 to 2.0, suitably from 0.02 to 1.8 and preferably from 0.025 to 1.5; and the degree of aromatic substitution (DSQ) can be from 0.001 to 1.0, usually from 0.01 to 0.8, suitably from 0.02 to 0.7 and preferably from 0.025 to 0.5. In case the anionic polymer contains cationic groups, the degree of cationic substitution (DSC) can be, for example, from 0 to 0.2, suitably from 0 to 0.1 and preferably from 0 to 0.05, the anionic polymer having an overall anionic charge. Usually the anionic charge density of the anionic polymer is within the range of from 0.1 to 6.0 meqv/g of dry polymer, suitably from 0.5 to 5.0 and preferably from 1.0 to 4.0.
The cationic organic polymer having an aromatic group and the anionic polymer having an aromatic group of the sizing promoter can be added to the aqueous suspension (stock) in any order separately from the addition of the sizing dispersion and in amounts which can vary within wide limits depending on, inter alia, type of stock, salt content, type of salts, filler content, type of filler, point of addition, etc. Generally the polymers are added in an amount that give better sizing than is obtained when not adding them and usually the cationic organic polymer is added to the stock prior to adding the anionic polymer. The cationic polymer is usually added in an amount of at least 0.001%, often at least 0.005% by weight, based on dry stock substance, whereas the upper limit is usually 3% and suitably 2.0% by weight. The anionic polymer is usually added in an amount of at least 0.001%, often at least 0.005% by weight, based on dry stock substance, whereas the upper limit is usually 3% and suitably 1.5% by weight.
Apart from the cationic organic polymer and the anionic polymer the sizing promoter may contain other compounds which improve the sizing efficiency such as anionic microparticulate materials, e.g., silica-based particles and clays of smectite type, low molecular weight cationic organic polymers, aluminium compounds like alum, aluminates, aluminium chloride, aluminium nitrate and polyaluminium compounds, such as poly-aluminium chlorides, polyaluminium sulphates, polyaluminium compounds containing both chloride and sulphate ions, polyaluminium silicate-sulphates and mixtures thereof, anionic vinyl addition polymers and combinations thereof.
The process of the invention is preferably used in the manufacture of paper from a suspension containing cellulosic fibres, and optional fillers, having a high conductivity. Usually, the conductivity of the stock is at least 0.20 mS/cm, suitably at least 0.5 mS/cm, preferably at least 3.5 mS/cm. Very good sizing results have been observed at conductivity levels above 5.0 mS/cm and even above 7.5 mS/cm. Conductivity can be measured by standard equipment such as, for example a WTW LF 539 instrument supplied by Christian Berner. The values referred to above are suitably determined by measuring the conductivity of the cellulosic suspension that is fed into or present in the headbox of the paper machine or, alternatively, by measuring the conductivity of white water obtained by dewatering the suspension. High conductivity levels mean high contents of salts (electrolytes), where the various salts can be based on mono-, di- and multivalent cations like alkali metals, e.g. Na+ and K+, alkaline earths, e.g. Ca2+ and Mg2+, aluminium ions, e.g. Al3+, Al(OH)2+ and polyaluminium ions, and mono-, di- and multivalent anions like halides, e.g., Clxe2x88x92, sulfates, e.g. SO42xe2x88x92 and HSO4xe2x88x92, carbonates, e.g. CO32xe2x88x92 and HCO3xe2x88x92, silicates and lower organic acids. The invention is particularly useful in the manufacture of paper from stocks having high contents of salts of di- and multivalent cations, and usually the cation content is at least 200 ppm, suitably at least 300 ppm and preferably at least 400 ppm. The salts can be derived from the cellulosic fibres and fillers used to form the stock, in particular in integrated mills where a concentrated aqueous fiber suspension from the pulp mill normally is mixed with water to form a dilute suspension suitable for paper manufacture in the paper mill. The salt may also be derived from various additives introduced into the stock, from the fresh water supplied to the process, or be added deliberately, etc. Further, the content of salts is usually higher in processes where white water is extensively recirculated, which may lead to considerable accumulation of salts in the water circulating in the process.
The present invention further encompasses papermaking processes where white water is extensively recirculated (recycled), i.e. with a high degree of white water closure, for example where from 0 to 30 tons of fresh water are used per ton of dry paper produced, usually less than 20, suitably less than 15, preferably less than 10 and notably less than 5 tons of fresh water per ton of paper. Recirculation of white water obtained in the process suitably comprises mixing the white water with cellulosic fibres and/or optional fillers to form a suspension to be sized; preferably it comprises mixing the white water with a suspension containing cellulosic fibres, and optional fillers, before the suspension enters the forming wire for sizing.
Further additives which are conventional in papermaking can of course be used in combination with the additives according to the invention, such as, for example, additional dry strength agents, wet strength agents. The cellulosic suspension, or stock, can also contain mineral fillers of conventional types such as, for example, kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, ground marble and precipitated calcium carbonate.
The process of this invention is used for the production of paper. The term xe2x80x9cpaperxe2x80x9d, as used herein, of course include not only paper and the production thereof, but also other sheet or web-like products, such as for example board and paperboard, and the production thereof. The process can be used in the production of paper from different types of suspensions of cellulose-containing fibres and the suspensions should suitably contain at least 25% by weight and preferably at least 50% by weight of such fibres, based on dry substance. The suspensions can be based on fibres from chemical pulp such as sulphate, sulphite and organosolv pulps, mechanical pulp such as thermomechanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp, from both hardwood and softwood, and can also be based on recycled fibres, optionally from de-inked pulps, and mixtures thereof. The invention is particularly useful in the manufacture of paper from suspensions based on pulps comprising recycled fibres and de-inked pulp, and the content of cellulosic fibres of such origin can be up to 100%, suitably from 20% to 100%.
The invention is further illustrated in the following Examples which, however, are not intended to limit the same. Parts and % relate to parts by weight and % by weight, respectively, unless otherwise stated.